ELECTROPLATING Electroplating is the application of a metal coating to a metallic or other conducting surface by an electrochemical process. The article to be plated (the work) is made the cathode (negative electrode) of an electrolysis cell through which a direct electric current is passesd. The article is immersed in an aqueous solution (the bath) containing the required metal in an oxidised form, either as an aquated cation or as a complex ion. The anode is usually a bar of the metal being plated. During electrolysis metal is deposited on to the work and metal from the bar dissolves: at cathode Mz+(aq) + ze- → M(s) at anode M(s) → Mz+(aq) + ze- Faraday's laws of electrolysis govern the amount of metal deposited. Articles are elecroplated to (i) alter their appearance; (ii) to provide a protective coating; (iii) to give the article special surface properties; (iv) to give the article engineering or mechanical properties. INTRODUCTION Electrodeposition is the application of metallic coatings to metallic or other conductive surfaces by electrochemical processes. Electroplating is both an art and a science. Although based on several technologies and sciences, including chemistry, physics, chemical and electrical engineering, metallurgy, and perhaps others, it retains in some ways the aspects of an art, in which experience is the only teacher. In fact, of course, all the sciences have elements of art which can be learned only by experience; all the reading of textbooks on chemistry will not produce a chemist. No text on electroplating will produce an expert electroplater; there is no substitute for experience and what is somewhat inelegantly termed know-how. THE PURPOSES OF ELECTOPLATING Some of the purposes for which articles are electroplated are: (1) Appearance (2) Protection (3) Special surface properties (4) Engineering or mechanical properties. The distinctions between these aims are not, of course, clear-cut and there are many overlapping categories. A deposit applied purely for appearance must be, at least to some extent, protective as well. But the classification is convenient. Some finishes are purely decorative. Many objects meant to be used indoors, in a dry environment and where danger of corrosion is slight, are nevertheless finished with lacquers, paints and electroplated coatings for purely aesthetic reasons. The very thin layer of gold applied to some articles of inexpensive jewellery has little or no protective value; it is there principally to attract a potential buyer. There are many applications of electroplating, some of them of increasing importance at present, in which neither corrosion prevention or decorative appeal is the reason for using a VIII-Metals-G-Electroplating-1 finish. Copper is an excellent conductor of electricity and is therefore basic to such items as printed circuits and communications equipment. It does, however, quickly form tarnish films that interfere with joining operations such as soldering and that also render contact resistances unacceptably high in relays and switches. To make soldering easier, coatings of tin or tin-lead alloys are often applied to copper, and for better contacts overplates of gold are frequently required. Other surface properties may call for modification; if light reflection is important, a silver or rhodium plate may be necessary. In wave guides for radar, high electrical conductivity is the most important criterion, and silver is the preferred coating. Good bearing properties may require coatings of tin, lead or indium. If a hard surface is required, chromium or nickel usually will serve. These few examples illustrate another use of metal finishing; to modify the surface properties, either physical or chemical, to render them suitable for the intended use. Although the answer may be obvious, we may pause momentarily to consider this question: if these coating metals are necessary to provide the article with the desired properties, why go through the somewhat complicating process of electroplating? Why not simply manufacture the article out of the desired metal in the first place? Usually the answer is cost or availability, and, in some cases, the properties of the metals concerned. An all-platinum chemical reaction vessel of practical production size would be prohibitively expensive; but a steel vessel, clad with a relatively thing layer of platinum, serves the purpose at far lower cost. An all-nickel automobile bumper would render the car a luxury for the rich, aside from the fact that the required amount of nickel would probably be unobtainable. A tin can made entirely of tin would not only be more expensive than the good inside, but would also have no physical strength; tin is a very soft and weak metal. Chromium in massive form is almost impossible to work into useful shapes. In summary electroplating allows the use of relatively inexpensive metals like steel and zinc for the bulk of the article, while affording to the exterior the selected properties of the coating chosen. THE ELECTROLYSIS CELL The components of the cell The physical embodiment of an electroplating process consists of four parts: 1 The external circuit, consisting of a source of direct current (dc), means of conveying this current to the plating tank, and associated instruments such as ammeters, voltmeters, and means of regulating the voltage and current at their appropriate values. 2 The negative electrodes or cathodes, which are the material to be plated, called the work, along with means of positioning the work in the plating solution so that contact is made with the current source. 3 The plating solution itself, almost always aqueous, called by platers the "bath"; 4 The positive electrodes, the anodes, usually of the metal being plated but sometimes of a conducting material which serves merely to complete the circuit, called inert or insoluble anodes. The plating solution, of course, is contained in a tank, which must be of a material appropriate to the solution it contains: often plain mild steel for alkaline solutions, and of steel lined with resistant material for acid solutions. Such linings may be of rubber, various plastics, or even glass or lead. VIII-Metals-G-Electroplating-2 The typical plating tank will have three bare copper or aluminium conductors running down its length; these are called bus bars, and they are insulated from the tank itself by various means such as ceramic insulators. The two outside bars are connected to the positive side of the dc source, and on them are hung the anodes, usually by means of hooks. The central bus bar is connected to the negative side of the dc source and holds the work, usually held on racks which are similarly hung on the cathode bar by hooks. The racks themselves are so constructed as to hold one or many parts, depending on their size and shape, and are often custom-made for the particular work being processed. The racks usually are covered with insulating material except where they make contact with the work and the cathode bus bar. When the work consists of many small parts (screws, nuts, small electric connectors, and the like) which do not lend themselves to being hung individually on plating racks, they may be placed in bulk in a barrel, which takes the place of the cathode and is rotated in the plating bath so that all parts at some time come into contact with a cathode placed inside the barrel. The barrel has holes, too small to permit the parts to fall out but large enough to permit fairly good circulation of the solution and passage of the electrolytic current. Barrels are of many types; some are self-contained (oblique barrels) and hold the solution, the anode, and the cathode contact, thus dispensing with a plating tank altogether. Barrels meant to be inserted into a plating tank may be of many shapes and of many materials, and the cathode contacts may be so-called danglers, buttons or of other forms. Barrel plating is no different in principle from plating on racks, though it has its own problems of design and plate distribution. Ingredients of a Plating Bath Every plating bath contains ingredients which serve one or more of the following functions: 1 To provide a source of the metal or metals being deposited. 2 To form complexes with ions of the depositing metal 3 To provide conductivity. 4 To stabilise the solution e.g. against hydrolysis. 5 To act as a buffer to stabilise the pH. 6 To modify or regulate the physical form of the deposit. 7 To aid in dissolving the anodes. 8 To modify other properties, either of the solution or of the deposit, peculiar to the specific case. There are two main purpose of forming complex ions of certain cations: 1 To stabilise the cation. Some metal cations are not stable in the simple aquated form, e.g. gold. They are much more stable when complexed to some ligand. The presence of the ligand lowers the concentration of the free (aquated) ion. 2 To hold the aquated form at suitably low concentration allowing control of the evenness of plating. - 2- The cyanide ion, CN , is a common ligand forming complex ions such as Zn(CN)4 , 2- - - Cu(CN)4 , Ag(CN)2 and Au(CN)2 . The Plating Metals Most electroplating coatings fall into one of the following six categories: 1 Sacrificial coatings, used primarily for protection of the basis metal, usually iron and steel (sometimes call anodic coatings, meaning that electrochemically they are anodic to the substrate). Sacrificial denotes that the coatings "sacrifice" themselves in the act of protecting the basis metal. VIII-Metals-G-Electroplating-3 2 Decorative protective coatings, used primarily for adding attractive appearance to some protective qualities. 3 Engineering coatings - a rather miscellaneous group whose members are used for specific properties imparted to the surface, such as solderability, wear resistance, reflectivity, conductivity, and many others.